Chs chj



U '1: d S P t t O m g a Patented May 18, 1955 3,184,459 Table-Cont1nued 3-(p-TRIAZINYLAMlN0-PHENYL)- COUMARIN (IQWOUNDS X Y Z Edgar Siegel, Leverkusen, and Heinrich Gold, Cologne- Stammheim, Germany, assignors to Farhenfahriken 5 Bayer Aktiengeselischaft, Leverkusen, Germany, a C1 H H German corporation No Drawing. Filed July 10, 1962, Ser. No. 208,953 Claims priority, application Germany, Sept. 11, 1961, O1 H H F 34,900 4 Claims. (Cl. 260-2495) CH3 CH3 The present invent-ion relates to coumarin compounds; C] 02 H more particularly it concerns 3-(p-triazinylamino-phenyD- couma-rin compounds of the general formula 1 G1 N(C2H5)2 0 f N or N H o1 CHM. 0 R2 N\ OCH:5 OCH3 H O OCH3 N(CzH )z H 0oH; N H H wherein R and R stand independently for hydrogen or a lower alkyl radical, eg for the methyl or ethyl radical, 5 While X and Y represent independently halogen, optio-n- *OOHK H H ally substituted alkoxy or aryloxy groups, alkyl merca-pto or aryl mercapto groups, the amino group or radicals of CH1 CH3 optionally substituted primary or secondary amines, the oc N(02H5)z 11, benzene nuclei A and B being possibly further substi- H tuted, e.g. by halogen or by alkyl, cyano, alkylsulfone, sulfonamide, carboxyl or su-lfonic acids. H

Representatives of the coumarin compounds of the present invention are shown in the following table; in H H H this table Z indicates the atom or atomic grouping in the 7-pos1t1on of the coumarin system. H H n H TABLE CHa OH CH5 CH3 X Y Z 40 The production of the coumarin compounds of the C1 NH2 H present invention from the starting components can be 01 NHCHs H carried out in known manner, egg. by reaction of op- 01 H tionally substituted 3-(p-arninophenyl)-coumarins with halogen triazines, if desired With further exchange of re- 01 NH C3H7(D) H maining halogen atoms by appropriate substituents. o1 NHC4H9(n) H The ooumarin compounds of the present invention can 01 NH CH2 UH (CH3)2 H be used as optical brightening agents; for this purpose they can be applied in the usual Way, for example in 01 NH G"H2 H the form of solutions in Water or in organic solvents or G1 -N(0H3)i.- H in the form of aqueous dispersions; they can also be 01 N(C2H5)2 H applied together with detergents. Furthermore they can be incorporated as brightening agents in spinning or cast- /C2H5 ing compositions for the production of artificial fibres, 01 H threads, foils or other shapes.

\ The parts in the following examples given by way of illustration of the present invention are parts by Weight.

Example 1 To a solution of 8 parts of cyanuric chloride in 40 parts of acetone, a solution of 10.6 parts of 3-(p-aminopheny1)-coumarin in 235 parts of acetone is added at C1 H 5 0-5 C. The mixture is then treated with 50 parts of ice and by gradual addition of a 16% soda solution brought to a pH value of 6. The reaction mixture is thereupon treated with 11.05 parts of N-ethyl-cyclohexylamine, stirred for 10 to 15 hours at room temperature and then heated for 30 minutes to 50 C. The acetone is then or -16] H distilled off, the residue diluted with Water and the precipitated pale yellow product filtered off, washed with water and dried. After recrystallizing from a mixture of benzene and light benzine the resulting coumarin compound which corresponds to the formula o N l \O/ melts at 219 C.

Example 2 l Cl mus obtained and recrystallised from glycol monomethyl ether acetate, lies at 218 C.

Example 3 A solution of 7.9 parts of 2,4-dimethoxy-6-chlorotriazine in parts of acetone is mixed with a solution of 10.6 parts of 3-(p-aminophenyl)-cournarin in 235 parts of acetone, the mixture treated with parts of water 7 and heated while stirring for 12 hours at C.; the hydrochloric acid thus formed is'continuously neutralised 35 with added soda. The acetone is then distilled off, the residue diluted with water, the reaction product which crystallized out filtered off and washed first with Water; and then with methanol. After recrystallising from glycol monomethyl ether acetate the coumarin compound which 40 corresponds to the formula V N I -Nn-c 0-0011. I 00- I OCH melts at 221 c.

Example 5 In a washing bath containing per litre 5 g. of a commercial mild or coarse detergent and 0.05 g. of the coumarin compound of Example 2 as brightening agent, a fabric of polyester fibres is treated for 30 minutes at 95100 C. using a goods-to-liquor ratio of 1:20. After rinsing and drying the fabric shows a brightening which is very fast to light.

Example 6 A solution of 5 parts of the coumarin compound of Example 3 in 100 parts of dimethyl formamide is poured into a cold solution prepared by dissolving l00 parts of a mixture consisting of a fatty alcohol .sulfonate and a fatty alcohol polyglycol ether in 100,000 parts of Water.

7 O l l wherein R and R are members selected from the group consisting of hydrogen and lower alkyl; X is a member selected from the group consisting of chloro, lower alkoxy, amino, lowerdialkylamino,

V U CH3\CH3 Y is a member selected from the group consisting of amino, alkyl-amino, di-lower-alkyl-amino, lower alkyl-cyclohexyl amino, dicyclohexyl amino, lower alkoxy,

N s02 and -N n Al li Alk wherein Alk is defined as lower alkyl; and the benzene nuclei, A, corresponding to the 7-position of the coumarin system, has a substituent grouping selected from the group consisting of hydrogen, methyl and chloro.

2. The coumarin compound of the formula 1 3. The coumarin compound of the formula 4. The coumarin compound of the formula V I OGH 518,213 11/55 Canada. 7 a 835,719 5/60 Great Britain.

IRVING MARCUS, Primary Examiner. WALTER A. MODANCE, Examiner. 

1. A COMPOUND OF THE FORMULA 